TWI419913B - Flame-retardant polyamide composition - Google Patents

Description

Flame retardant polyamine composition

This invention relates to a flame retardant polyamine composition.

The material constituting the electronic component previously uses a polyamide resin which can be heat-melted and formed into a predetermined shape. Generally, polyamine which is widely used may, for example, be nylon 6, nylon 66 or the like. The aliphatic polyamine has good formability, but on the other hand, it does not have sufficient heat resistance as a raw material for manufacturing a surface-encapsulated part, for example, which is exposed to a high temperature such as a reflow soldering step. Connector.

Due to such a background, nylon 46 was developed as a polyamine having high heat resistance. However, there is a problem that the water absorption rate of the nylon 46 is high, and the electronic component formed by using the nylon 46 resin composition causes dimensional change due to water absorption. When the molded body absorbs water, there arises a problem that foaming, so-called expansion, and the like are caused by the heating of the reflow soldering step. In particular, in recent years, from the viewpoint of environmental issues, a surface encapsulation method using lead-free solder is being adopted. Lead-free solder has a higher melting point than previous lead solders, so the package temperature must also rise by 10 ° C ~ 20 ° C. Therefore, nylon 46 has difficulty in use.

In response to this, an aromatic polyamine derived from an aromatic dicarboxylic acid such as terephthalic acid and an aliphatic alkyl diamine has been developed. The aromatic polyamine is characterized in that it is more excellent in heat resistance and low water absorbability than an aliphatic polyamine such as nylon 46. In addition, aromatic polyamines can have higher rigidity than nylon 46, but sometimes they are not sufficiently tough. Sexual problem. In particular, if the toughness of the connector material for a fine PACE connector is insufficient, cracking and whitening of the product may occur during terminal insertion and insertion and removal. Therefore, it is desirable to develop materials with higher toughness.

If the proportion of the polyamide resin is increased and the amount of the flame retardant is decreased, the toughness can be improved. However, in electronic parts such as connectors, it is often required to have a high flame retardancy or fire resistance of V-0 as specified in Underwriters Laboratories Standard UL94. Therefore, there is a need for a material that does not impair flame retardancy and has high toughness.

On the other hand, a known flame retardant is generally a halogen-containing flame retardant such as brominated polyphenylene ether, brominated polystyrene, polybrominated styrene or the like. However, the halogen compound is accompanied by the generation of a toxic gas hydrogen halide upon combustion. Global Warming is a problem, and it is important to develop a flame retardant with high heat resistance and halogen-free type. Among such flame retardants, the use of phosphinates is attracting attention (refer to Japanese Patent Laid-Open Publication No. 2006-522842, International Publication No. 2005/033192, International Publication No. 2005/035664, International Publication No. Booklet No. 2005/121234, Japanese Patent Laid-Open No. 2007-023206.

[The problem that the invention wants to solve]

However, in the prior art, although the flame retardancy is ensured, the solder reflow heat resistance is insufficient, the mechanical properties such as toughness are insufficient, or the fluidity required for forming a small electronic component is poor, and it cannot be said that all the characteristics are satisfied.

The present invention provides a flame-retardant polyamine composition which is a halogen-free flame-retardant polyamine composition which does not generate a halogen compound even when burned, and which is excellent in thermal stability at the time of molding under high temperature conditions. The flame retardancy, fluidity, and toughness are high, and the heat resistance of the reflow soldering step in the surface package using lead-free solder is also good.

The inventors of the present invention have conducted intensive studies in view of the above-described circumstances, and have found that a flame-retardant polyamine composition comprising a specific polyamine resin, a phosphonium salt compound as a flame retardant, and a specific aliphatic metal salt is in a form stability, The present invention is excellent in flame retardancy, fluidity, and toughness, and is excellent in heat resistance in a reflow soldering step in a surface package using lead-free solder.

That is, the first invention of the present invention relates to a flame-retardant polyamine composition as shown below, and a molded article thereof.

[1] A flame-retardant polyamine composition comprising 20 wt% to 80 wt% of a polyamide resin (A) and 10 wt% to 20 wt% of a flame retardant having no halogen group in a molecule ( B), 0.05 wt% to 1 wt% of a fatty acid metal salt (C), and 0 wt% to 50 wt% of a reinforcing material (D); The flame retardant (B) is a metal phosphinate, and the fatty acid metal salt (C) is a lithium salt of montan acid, behenic acid or stearic acid. One or a mixture of two or more of a calcium salt, a barium salt, a zinc salt or an aluminum salt (excluding calcium stearate and aluminum stearate).

[2] The flame-retardant polyamine composition according to [1], wherein the polyamine resin (A) comprises a polyfunctional carboxylic acid component (a-1) and a carbon number of 4 to 25 Functional amine component unit (a-2), 60 mol% to 100 mol% of the polyfunctional carboxylic acid component unit (a-1) is a terephthalic acid component, and 0 mol% to 40 mol% is an aromatic polyfunctional carboxylic acid component other than terephthalic acid. 0 mol% to 40 mol% is an aliphatic polyfunctional carboxylic acid component having 4 to 20 carbon atoms.

[3] The flame-retardant polyamine composition according to [1] or [2], wherein the polyamine resin (A) has a melting point of 280 ° C to 340 ° C and is determined in concentrated sulfuric acid at 25 ° C. The ultimate viscosity [η] is from 0.5 dl/g to 0.95 dl/g.

Further, the second invention of the present invention relates to a method for producing a flame-retardant polyamine composition as shown below.

[4] A method for producing a flame-retardant polyamine composition according to any one of [1] to [3], which comprises: In the polymer of the amine resin (A), a step of mixing the metal phosphinate (B) and the metal salt of the fatty acid (C), and a step of extruding the above mixture in a molten state.

[5] A method for producing a flame-retardant polyamine composition according to any one of [1] to [3], comprising: preparing to contain a poly a resin composition of a guanamine resin (A) and a flame retardant (B), and optionally a reinforcing material (D), a step of adding a fatty acid metal salt (C) to the above resin composition; and adding the above fatty acid The above resin composition of the metal salt (C) is subjected to a step of injection molding.

The flame-retardant polyamine composition of the present invention is halogen-free, and has excellent mechanical properties such as toughness, heat resistance in the solder reflow step, and particularly fluidity. Moreover, it has high thermal stability at the time of forming. Therefore, the molded article obtained from the flame-retardant polyamine composition of the present invention does not generate hydrogen halide upon combustion, and is excellent in thermal stability, flame retardancy, fluidity, and toughness during molding, and uses lead-free solder. The heat resistance required for the surface package is also excellent.

Therefore, it is suitable for the flame-retardant polyamine composition of the present invention to produce an electronic component such as a thin-walled connector having a short distance between the terminals of the connector, or a surface-sealing method using a high-melting-point solder such as lead-free solder. Assembly parts. In addition, it can also reduce the environmental load.

The above and other objects, features and advantages of the present invention will become more <RTIgt;

1. The flame retardant polyamide resin composition of the present invention

As described above, the flame-retardant polyamide resin composition of the present invention comprises a polyamine resin (A), a flame retardant (B) having no halogen group in the molecule, and a fatty acid metal salt (C).

Polyamide resin (A) The polyamine resin (A) contained in the composition of the present invention contains a polyfunctional carboxylic acid component unit (a-1) and a polyfunctional amine component unit (a-2).

Polyfunctional carboxylic acid component unit (a-1) The polyfunctional carboxylic acid component unit (a-1) constituting the polyamine resin (A) is preferably 60 mol% to 100 mol% of a terephthalic acid component unit, 0 The mol%~40 mol% is an aromatic polyfunctional carboxylic acid component unit other than terephthalic acid, and 0 mol% to 40 mol% is an aliphatic polyfunctional carboxylic acid component unit having 4 to 20 carbon atoms.

The content of the terephthalic acid component unit is 60 mol% to 100 mol%, preferably 60 mol% to 70 mol%, based on the total of the polyfunctional carboxylic acid component unit (a-1). Further, the content of the aromatic polyfunctional carboxylic acid component unit other than terephthalic acid is 0 mol% to 40 mol%, preferably 0, based on the total of the polyfunctional carboxylic acid component unit (a-1). Mol%~30 mol%, more preferably 0 mol%~10 mol%.

Examples of the aromatic carboxylic acid component unit other than terephthalic acid include isophthalic acid, 2-methylterephthalic acid, naphthalene dicarboxylic acid, phthalic anhydride, trimellitic acid, and pyromellitic acid. And trimellitic anhydride, pyromellitic dianhydride, etc., especially isophthalic acid is preferred. Further, the aromatic carboxylic acid component units other than terephthalic acid may be used singly or in combination of two or more kinds. In the case where a trifunctional or trifunctional or higher polycarboxylic acid component unit is contained, it is necessary to make it a non-gelling content of the polyamidamide resin, and specifically, it is preferably a unit with respect to the total carboxylic acid component. It is 10 mol% or less.

When the ratio of the aromatic polyfunctional carboxylic acid component unit is increased, it is seen that the moisture absorption amount of the polyamide resin is lowered, and the reflow heat resistance tends to be improved. In particular, in the case of using the reflow soldering step of the lead-free solder, it is preferred to make the terephthalic acid component unit 60 mol% or more with respect to the total of the polyfunctional carboxylic acid component units.

In addition, the amount of aromatic polyfunctional carboxylic acid component other than terephthalic acid The smaller the content becomes, the higher the crystallinity of the polyamide resin becomes. Therefore, it is understood that the mechanical properties of the resin molded article tend to be high in toughness.

The content of the aliphatic polyfunctional carboxylic acid component unit having 4 to 20 carbon atoms is 0 mol% to 40 mol%, preferably 30, based on the total of the polyfunctional carboxylic acid component unit (a-1). Mol%~40 mol%.

The aliphatic polyfunctional carboxylic acid component unit may be derived from an aliphatic polyfunctional carboxylic acid compound having 4 to 20 carbon atoms, preferably 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. Examples of such aliphatic polyfunctional carboxylic acid compounds include Adipic acid, Suberic acid, Azelaic acid, Sebacylic acid, Decanedicarboxylic acid (Decanedicarboxylic acid). Acid), undecanedicarboxylic acid, dodecanedicarboxylic acid, and the like. From the viewpoint of improving mechanical properties, adipic acid is particularly preferred.

In addition, a trifunctional or trifunctional or higher polyfunctional carboxylic acid compound may be suitably used as needed, but it should be added in a non-gelling amount of the polyamidamide resin, specifically, it must be made relative to the carboxylic acid. The total of the constituent units is 10 mol% or less.

Polyfunctional amine component unit (a-2) The polyfunctional amine component unit (a-2) constituting the polyamide resin (A) includes a polyfunctional linear group having 4 to 25 carbon atoms, preferably 4 to 8 carbon atoms. Amine component unit. More preferably, the polyfunctional amine component unit (a-2) includes a linear polyfunctional amine component unit having 4 to 8 carbon atoms.

Specific examples of the linear polyfunctional amine component unit include 1,4-butanediamine (1,4-Diaminobutane), 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1, 11-undecanediamine, 1,12-dodecanediamine and the like, among which 1,6-hexanediamine is preferred.

Further, specific examples of the linear aliphatic diamine component unit having a branched chain include 2-methyl-1,5-pentanediamine, 2-methyl-1,6-hexanediamine, and 2-methyl- 1,7-heptanediamine, 2-methyl-1,8-octanediamine, 2-methyl-1,9-nonanediamine, 2-methyl-1,10-nonanediamine, 2-methyl The base-1,11-undecanediamine or the like is preferably 2-methyl-1,5-pentanediamine or 2-methyl-1,8-octanediamine.

The polyfunctional amine component unit (a-2) may also contain an alicyclic polyfunctional amine component unit. Examples of the alicyclic polyfunctional amine component unit include 1,3-diaminocyclohexane, 1,4-cyclohexanediamine, and 1,3-bis(aminomethyl) ring. Hexane, 1,4-bis(aminomethyl)cyclohexane, Isophorone Diamine, Piperazine, 2,5-dimethylpiperazine, bis(4-amine Methylcyclohexyl)methane, bis(4-aminocyclohexyl)propane, 4,4'-diamino-3,3'-dimethyldicyclohexylpropane, 4,4'-diamino-3, 3'-Dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-dimethyldicyclohexylmethane, 4,4'-diamino -3,3'-dimethyl-5,5'-dimethyldicyclohexylpropane, α,α'-bis(4-aminocyclohexyl)-p-diisopropylbenzene, α,α'- Bis(4-Aminocyclohexyl)-m-isopropylidenebenzene, α,α'-bis(4-aminocyclohexyl)-1,4-cyclohexane, α,α'-bis(4-amine A component unit derived from an alicyclic diamine such as a cyclohexyl)-1,3-cyclohexane. Among them, the alicyclic diamine component unit is preferably from 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, bis(aminomethyl)cyclohexane, bis(4-amino ring). Hexyl) methane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane derived component unit, particularly preferably from 1,3-cyclohexanediamine, 1,4-cyclohexane Diamine, double (4- A component unit derived from an alicyclic diamine such as aminocyclohexyl)methane, 1,3-bis(aminocyclohexyl)methane or 1,3-bis(aminomethyl)cyclohexane.

In the case where the polyfunctional amine component unit (a-2) includes a trifunctional or trifunctional or higher polyfunctional amine component unit, it is necessary to make the ratio thereof not to gelatinize the resin, specifically Preferably, it is 10 mol% or less based on the total of the amine component units.

The polyamidamide resin (A) of the present invention has an ultimate viscosity [η] of from 0.5 dl/g to 1.2 dl/g, preferably from 0.65 dl/g to 0.95 dl, as measured in a temperature of 25 ° C and 96.5% sulfuric acid. g, more preferably 0.75 dl/g to 0.90 dl/g. When the ultimate viscosity [η] is within this range, a polyamide composition having excellent fluidity, reflow heat resistance, and high toughness can be obtained.

It is preferred that the polyamide resin (A) is crystalline and has a melting point. The melting point of the polyamide resin (A) is preferably from 280 ° C to 340 ° C, more preferably from 300 ° C to 340 ° C, still more preferably from 315 ° C to 330 ° C. The melting point of the polyamide resin (A) can be measured by a differential scanning calorimeter (DSC), and the endothermic peak of melting at a temperature of 10 ° C / min is taken as the melting point (Tm).

The polyamidamide resin having the above melting point has particularly excellent heat resistance. In addition, if the melting point is 280 ° C or more, especially 300 ° C or more, especially 315 ° C ~ 330 ° C, even in the lead-free reflow soldering step, especially when using lead-free solder with high melting point Also, sufficient heat resistance can be obtained. On the other hand, if the melting point of the polyamide resin is lower than the decomposition point (350 ° C) of the polyamine, the temperature is 340 ° C or less, and no foaming, decomposition gas or molding occurs during molding. Color change And so on. Therefore, sufficient thermal stability can be obtained.

Flame retardant (B) The flame retardant (B) contained in the flame-retardant polyamine composition of the present invention is added for the purpose of reducing the combustibleness of the resin. Further, the flame retardant (B) has no halogen group in the molecule.

In order to impart heat resistance, flame retardancy, fluidity, and heat resistance which can withstand the reflow temperature of lead-free solder at a temperature of 280 ° C or higher at a temperature of 280 ° C or higher, the flame retardant polyamine composition of the present invention is imparted. Further, the toughness is equal to or higher than that of the nylon 46, and the flame retardant (B) is a phosphinate compound. It is preferred that the flame retardant (B) is a phosphinic acid metal salt compound.

The phosphinate compound is represented by, for example, a compound represented by the following formula (I) and/or formula (II).

In the formulae (I) and (II), R ¹ and R ² may be the same or different and each represents a linear or branched C ₁ -C ₆ -alkyl group, an aryl group or a phenyl group. R ³ represents a linear or branched C ₁ -C ₁₀ -alkylene group, a C ₆ -C ₁₀ -exylaryl group, a C ₆ -C ₁₀ -alkyl extended aryl group, or a C ₆ -C ₁₀ -aryl group. Base alkyl group. M represents a calcium atom, a magnesium atom, an aluminum atom and/or a zinc atom. m is 2 or 3, n is 1 or 3, and x is 1 or 2.

More specific examples of the phosphinate compound include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, and ethylmethylphosphinic acid. Calcium, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, magnesium diethylphosphinate, diethylphosphinium Aluminum acid, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyl-propylphosphinate, zinc methyl-n-propylphosphinate , methyl bis(methylphosphinic acid) calcium, magnesium bis(methylphosphinic acid), aluminum bis(methylphosphinic acid), zinc dimethyl (methylphosphinic acid), benzene-1,4 -(Dimethylphosphinic acid) calcium, benzene-1,4-(dimethylphosphinic acid) magnesium, benzene-1,4-(dimethylphosphinic acid) aluminum, benzene-1,4-( Dimethylphosphinic acid)zinc, calcium methylphenylphosphonate, magnesium methylphenylphosphonate, aluminum methylphenylphosphinate, zinc methylphenylphosphonate, calcium diphenylphosphonate, diphenyl Magnesium phosphinate, aluminum diphenylphosphinate, zinc diphenylphosphinate, etc., preferably calcium dimethyl phosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, ethyl methyl Calcium phosphonate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, calcium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, more preferably Aluminum diethylphosphinate.

The phosphinate compound as the flame retardant (B) can be easily obtained from the market. Examples of the phosphinate compound available from the market include EXOLITOP 1230, OP1311, OP1312, OP930, OP935, and the like manufactured by Clariant (Japan).

Fatty acid metal salt (C)

Fatty acid metal salt contained in the flame retardant polyamine composition of the present invention The purpose of use of the compound (C) is to improve the fluidity of the resin at the time of injection molding. The fatty acid metal salt compound (C) is particularly effective in forming a high fluidity such as forming a thin-walled small electronic component. In particular, when the composition contains a polyamide resin (A) having a melting point of 300 ° C or more, the processing temperature is also 300 ° C or more, so that the fluidity of the resin and the gas during molding are taken into consideration. It is effective to use a specific fatty acid metal salt.

As the fatty acid metal salt (C), a known compound can be used. Examples of the fatty acid of the fatty acid metal salt (C) include montanic acid, behenic acid, stearic acid and the like. Examples of the metal salt of the fatty acid metal salt (C) include a lithium salt, a calcium salt, a barium salt, a zinc salt, an aluminum salt and the like. However, the fatty acid metal salt (C) does not contain calcium stearate and aluminum stearate. In order to balance the fluidity at the time of formation and prevent the generation of gas, preferred examples of the fatty acid metal salt (C) include a lithium salt of a montanic acid or a behenic acid, a calcium salt, a barium salt, a zinc salt, an aluminum salt, and more preferably. Examples include lithium or monic acid lithium salts, calcium salts, zinc salts. The fatty acid metal salt (C) may be one type or a mixture of two or more types.

Reinforcing material (D)

The flame-retardant polyamine composition of the present invention may also contain a reinforcing material (D). The reinforcing material (D) can be various inorganic fillers having a shape of a fiber, a powder, a pellet, a plate, a needle, a cloth, or a mad.

In more detail, the reinforcing material (D) may be cerium oxide, lanthanum aluminum oxide (Silica-alumina), alumina, calcium carbonate, titanium dioxide, talc, ash stone, diatomaceous earth, clay, kaolin, spherical Powdery or plate-like inorganic compounds such as glass, mica, gypsum, iron oxide, magnesium oxide and zinc oxide; Acicular inorganic compounds such as potassium titanate; glass fibers, potassium titanate fibers, metal-coated glass fibers, ceramic fibers, ash, carbon fibers, metal carbide fibers, metal hardened fibers, asbestos fibers, and boron fibers Inorganic fibers; aromatic polyamide fibers, organic fibers such as carbon fibers, and the like.

Fibrous fillers are particularly preferred as glass fibers. By making the reinforcing material (D) a glass fiber, the formability of the composition can be improved, and the tensile strength, flexural strength, and flexural modulus of the formed body formed of the thermoplastic resin composition can be improved. (Bending modulus of elasticity) and other heat resistance characteristics such as mechanical properties and heat distortion temperature. The average length of the glass fiber to be the reinforcing material (D) is usually in the range of 0.1 mm to 20 mm, preferably in the range of 0.3 mm to 6 mm, and the aspect ratio (L (average length of fiber) / D (average of fiber) The outer diameter)) is usually in the range of 10 to 5,000, preferably in the range of 2000 to 3,000.

The reinforcing material (D) may also be a mixture of two or more kinds of filling materials. Further, these fillers may be treated with a decane coupling agent, a titanium coupling agent or the like. For example, the surface treatment may be carried out using a decane-based compound such as vinyltriethoxysilane, 2-aminopropyltriethoxysilane or 2-glycidoxypropyltriethoxysilane.

The fibrous filler in the reinforcing material (D) may also be coated with a binder, preferably an acrylic, acrylic/maleic acid, epoxy or urethane system. A urethane/maleic acid modified system, a urethane/amine modified system compound. The above surface treatment agent may be used in combination with the above sizing agent. By using the above surface treating agent in combination with the above sizing agent, the fibrous filler and the group in the composition of the present invention can be improved. The combination of other components in the product is improved in appearance and strength characteristics are also improved.

Flame Retardant Auxiliary The flame retardant polyamine composition of the present invention may optionally contain a flame retardant aid. The flame retardant auxiliary may be a compound which is markedly improved by the use of a flame retardant in combination with a flame retardant. A well-known compound can be used for a flame retardant adjuvant. Specific examples of the flame retardant auxiliary include antimony trioxide, antimony Tetroxide, antimony pentoxide, sodium citrate and the like, 2ZnO. 3B ₂ O ₃ , 4ZnO. B ₂ O ₃ . H ₂ O, 2ZnO. 3B ₂ O ₃ . 3.5H ₂ O such as zinc borate, zinc stannate, zinc phosphate, calcium borate, calcium molybdate, zinc oxide, calcium oxide, barium oxide, aluminum oxide, tin oxide, magnesium oxide, aluminum phosphate, boehmite. Other examples of the flame retardant auxiliary agent include one or more phosphorus compounds selected from the group consisting of phosphoric acid, pyrophosphoric acid, and polyphosphoric acid, and one or more selected from the group consisting of melamine, melam, and melem. a salt of the compound or the like.

The flame retardant auxiliary agent may be used singly or in combination of two or more kinds.

Other additives The flame-retardant polyamine composition of the present invention may contain, in addition to the above components, a heat-resistant stabilizer, a weather-resistant stabilizer, a fluidity improver, or the like, which does not impair the object of the present invention. Various known composites such as plasticizers, tackifiers, static inhibitors, mold release agents, pigments, dyes, inorganic or organic fillers, nucleating agents, fiber reinforcements, carbon black, talc, clay, mica, etc. Compounding agent.

For example, the flame-retardant polyamine composition of the present invention may contain an additive such as an ion trapping agent which is generally used. Hydrotalcite is known as an example of an ion trapping agent. Further, when the flame-retardant polyamine composition of the present invention contains the above-mentioned fiber reinforcing agent, heat resistance, flame retardancy, rigidity, tensile strength, bending strength, and impact strength can be further improved.

Further, the flame-retardant polyamine composition of the present invention may contain other polymers within the range not detracting from the object of the present invention. Examples of other polymers include polyethylene, polypropylene, poly 4-methyl-1-pentene, ethylene. 1-butene copolymer, propylene. Ethylene copolymer, propylene. Polyolefins such as 1-butene copolymer, polyolefin elastomer, polystyrene, polyamide, polycarbonate, polyacetal, polyfluorene, polyphenylene ether, fluorocarbon resin (Fluorocarbon Resin), silicone resin (Silicone) Resin), Polyphenylene Sulfide (PPS), Liquid Crystal Polymer (LCP), Teflon (registered trademark), and the like. The flame-retardant polyamine composition of the present invention may also contain a modified body of polyolefin or the like. Examples of modified polyolefins include modified polyolefin elastomers modified with carboxyl groups, acid anhydride groups, amine groups, etc. (modified polyethylene, modified styrene-ethylene-butadiene-styrene copolymer (SEBS) And the like, etc., modified aromatic vinyl compound, conjugated diene copolymer or hydrogenated product thereof, modified ethylene, propylene copolymer, etc.).

[Flame retardant polyamine composition] The flame-retardant polyamine composition of the present invention is based on 100 parts by weight of the total amount of the polyamide resin (A), the flame retardant (B), the fatty acid metal salt (C), and the reinforcing material (D). Preferably, the polyamide resin (A) is contained in a proportion of 20% by weight to 80% by weight, preferably 40% by weight to 60% by weight. If When the amount of the polyamide resin (A) in the flame-retardant polyamine composition is 20% by weight or more, sufficient kinetic properties can be obtained, and if the polyfluorinated polyamine composition is aggregated When the amount of the guanamine resin (A) is 80% by weight or less, it may contain a sufficient flame retardant to obtain flame retardancy.

The content of the flame retardant (B) is preferably 10 wt% relative to the total amount of the polyamide resin (A), the flame retardant (B), the fatty acid metal salt (C), and the reinforcing material (D). 20 wt%, more preferably 13 wt% to 19 wt%. The content of the flame retardant (B) in terms of phosphorus content is 2 wt% to 5 wt%, preferably 3 wt% to 4.6 wt%. If the content of the flame retardant (B) in the flame retardant polyamide composition is 10 wt% or more, sufficient flame retardancy can be obtained, if the flame retardant polyamine composition is resistant When the content of the fuel (B) is 20% by weight or less, the fluidity at the time of molding, the toughness of the molded article, and the like, and the heat resistance of the reflow are not lowered.

The content of the fatty acid metal salt (C) is preferably 0.05 wt% relative to the total amount of the polyamide resin (A), the flame retardant (B), the fatty acid metal salt (C), and the reinforcing material (D). 1 wt%, more preferably 0.1 wt% to 0.8 wt%. When the content of the fatty acid metal salt (C) is within the above range, both the fluidity at the time of molding and the prevention of gas generation can be achieved. When the content of the fatty acid metal salt (C) in the flame-retardant polyamine composition is 0.05% by weight or more, it is possible to impart good fluidity to the polyamide resin composition. In addition, when the content of the fatty acid metal salt (C) in the flame-retardant polyamine composition is 1 wt% or less, the amount of gas generated during injection molding does not increase, which is preferable.

Relative to polyamine resin (A), flame retardant (B), fatty acid metal salt The total amount of (C), the content of the reinforcing material (D) is preferably from 0 wt% to 50 wt%, more preferably from 20 wt% to 45 wt%. When the content is 50% by weight or less, the fluidity at the time of injection molding is not lowered, which is preferable.

The content of the flame retardant auxiliary is preferably 0.5 wt% to 10% relative to the total amount of the polyamide resin (A), the flame retardant (B), the fatty acid metal salt (C), and the reinforcing material (D). The wt% is more preferably 0.5 wt% to 5 wt%, further preferably 1 wt% to 4 wt%.

Further, the flame-retardant polyamine composition of the present invention may contain any of the above-mentioned other additives within the range not impairing the object of the present invention.

It is preferred that the flame retardant polyamine composition of the present invention has a flammability rating of V-0 based on the UL94 standard. Further, it is preferred that the reflow heat resistance temperature after the moisture absorption at a temperature of 40 ° C and a relative humidity of 95% is from 250 ° C to 280 ° C, more preferably from 260 ° C to 280 ° C.

It is preferred that the flame retardant polyamine composition of the present invention has a mechanical property, that is, an index of toughness, a Breaking Energy of 50 mJ to 70 mJ, more preferably 52 mJ to 70 mJ. It is preferred that the flame-retardant polyamine composition is injection-molded in a bar-flow mold to have a flow length of 50 mm to 90 mm, more preferably 55 mm to 80 mm.

As described above, the flame-retardant polyamine composition of the present invention has excellent heat resistance required for surface encapsulation using lead-free solder, has high toughness equivalent to or higher than nylon 46, and has high melt fluidity and flame retardancy. And the material for forming stability is particularly suitable for use in electronic parts.

2. Method for preparing flame retardant polyamine composition

The flame-retardant polyamine composition of the present invention can be kneaded by a known resin. Manufacturing by hand. For example, a method may be employed in which each component is subjected to a Henschel mixer, a V-blender, a ribbon blender, a Tumbler blender, or the like. The mixing method or the method of granulating or pulverizing after further performing a melt-kneading using a uniaxial extruder, a multi-axis extruder, a kneader, a Banbury mixer or the like after mixing.

Further, although not particularly limited, the method for producing a flame-retardant polyamine composition can be roughly classified into the following two types according to a method of adding a fatty acid metal salt (C): 1) comprising a polyamide resin (A), a method in which a flame retardant (B), a fatty acid metal salt (C), and a composition of any reinforcing material (D) are melt-kneaded to obtain a polyamide resin composition; 2) is composed of the above polyamine resin A method of mixing the fatty acid metal salt (C) in the particles formed (which may also not contain the fatty acid metal salt (C)).

By using these methods, a composition excellent in the balance between the fluidity at the time of molding and the toughness of the molded article can be obtained, and in particular, the method of 2) can be used to obtain a composition excellent in fluidity at the time of molding even with the same composition. Things. The fatty acid metal salt (C) generally has lower heat resistance than the polyamide resin (A). Therefore, there is a tendency that a part of the fatty acid metal salt (C) is volatilized and removed from the composition during extrusion molding. Although it is possible to estimate the amount of volatilization and removal, and increase the amount of the material under the fatty acid metal salt (C), even if the amount is excessively increased, the viscosity is liable to occur or the heat resistance of the composition is lowered. That is, when the amount of the blank is the same, the addition method of 2) makes it easier to maintain the residual amount of the fatty acid metal salt (C) in the composition.

3.About the molded body and electronic parts materials

The flame-retardant polyamine composition of the present invention can be molded into various molded articles by a known molding method such as Compression Molding, Injection Molding, or Extrusion Molding.

The flame-retardant polyamine composition of the present invention is excellent in molding stability, heat resistance, and mechanical properties, and can be used in applications requiring such properties or in the field of precision molding. Specific examples include electronic components such as automotive electrical components (Electrical Component), current circuit breakers (Circuit Breakers), connectors, and light-emitting diodes (LED) reflective materials, and coiled tubes (Coil Bobbin). Various molding bodies such as a housing.

[Examples]

The invention will be more specifically described below based on the examples, but the scope of the invention is not limited by the examples. In the examples and comparative examples, the measurement and evaluation of each trait were carried out in the following manner.

[limit viscosity [η]] A sample solution was prepared by dissolving 0.5 g of a polyamide resin in 50 ml of a 96.5% sulfuric acid solution based on JIS K6810-1977. At 25 ± 0.05 ° C, the Ubbelohde viscometer was used to measure the number of seconds of the sample solution, and the ultimate viscosity was calculated according to the following formula.

[η]=ηSP/[C(1+0.205ηSP)] ηSP=(t-t0)/t0 [η]: ultimate viscosity (dl/g) ηSP: specific viscosity C: sample concentration (g/dl) t: seconds of sample solution flow (seconds) T0: blank (blank) seconds of sulfuric acid flow (seconds)

[melting point (Tm)] Using DSC7 (manufactured by Perkin Elemer Co., Ltd.), the temperature was first maintained at 330 ° C for 5 minutes, then at a rate of 10 ° C / min to 23 ° C, and then the temperature was raised at 10 ° C / min. The endothermic peak caused by the melting at this time was taken as the melting point.

[combustion test] Using a test piece of 1/32 吋 × 1/2 吋 × 5 制备 prepared by injection molding, a vertical burning test was conducted based on UL94 specification (UL Test No. UL94 proposed on June 18, 1991), and flame retardancy was evaluated. Sex.

Forming machine: Tuparl TR40S3A (manufactured by Sodick Plustech Co., Ltd.) Forming machine cylinder temperature: melting point of each polyamide resin +10 ° C Metal mold temperature: 120 ° C

[Reflow heat resistance test] A test piece prepared by injection molding and having a length of 64 mm, a width of 6 mm, and a thickness of 0.8 mm was subjected to humidity control (Humidity control) at a temperature of 40 ° C and a relative humidity of 95% for 96 hours.

Forming machine: Tuparl TR40S3A (manufactured by Sodick Plustech Co., Ltd.) Forming machine cylinder temperature: melting point of each polyamide resin +10 ° C Metal mold temperature: 100 ° C

The test piece subjected to the humidity control treatment as described above was placed on a glass epoxy substrate having a thickness of 1 mm. A temperature sensor is further disposed on the substrate. The obtained sample was placed in a hot air reflow type soldering machine (HOT AIR REFLOW SOLDERING MACHINE, AIS-20-82-C manufactured by Eightech Tectron Co., Ltd.), and the reflowing step of the temperature distribution shown in Fig. 1 was carried out.

As shown in Fig. 1, 1) the temperature is raised to a temperature of 230 ° C at a predetermined rate, 2) and then heated to a set temperature in 20 seconds (a is 270 ° C, b is 265 ° C, c is 260 ° C, d is 250 ° C, e is 240 ° C), 3) is cooled to 230 ° C. At this time, the maximum value of the set temperature at which the test piece was not melted and the foaming did not occur on the surface was obtained. The maximum value of the set temperature was determined as the reflow heat resistance temperature.

In general, the reflow heat-resistant temperature of the moisture-absorbing test piece tends to decrease as compared with the reflow temperature in the absolute dry state. Further, as the ratio of the polyamide resin/flame retardant dose is lowered, there is a tendency that the reflow heat resistance temperature is lowered.

[Bending test] A test piece prepared by injection molding and having a length of 64 mm, a width of 6 mm, and a thickness of 0.8 mm was allowed to stand at a temperature of 23 ° C for 24 hours under a nitrogen atmosphere. Then, a bending test was performed using a bending tester (manufactured by NTESCO Co., Ltd., AB5) under an environment of a temperature of 23 ° C and a relative humidity of 50%. The span is 26 mm and the bending speed is 5 mm/min. The bending strength, the amount of deformation, the modulus of elasticity, and the energy (toughness) required to break the test piece were measured.

Forming machine: Tuparl TR40S3A (manufactured by Sodick Plustech Co., Ltd.) Forming machine cylinder temperature: melting point of each polyamide resin +10 ° C Metal mold temperature: 100 ° C

[Flow length test (liquidity)] The injection molding was carried out using a bar-flow mold having a width of 10 mm and a thickness of 0.5 mm under the following conditions, and the flow length (mm) of the resin in the metal mold was measured.

Injection molding machine: Tuparl TR40S3A (manufactured by Sodick Plustech Co., Ltd.) Injection setting pressure: 2000 kg/cm ² Tank setting temperature: melting point of each polyamide resin + 10 ° C Metal mold temperature: 120 ° C

The polyamine resin (A), the flame retardant (B), the fatty acid metal salt (C), and the reinforcing material (D) used in the examples or the comparative examples are as follows.

[Polyuramine resin (A)] (polyamide resin (A-1)) Composition: dicarboxylic acid component unit (terephthalic acid: 62.5 mol%, adipic acid: 37.5 mol%), diamine component unit (1,6-hexanediamine: 100 mol%) Ultimate viscosity [η]: 0.8 dl/g Melting point: 320 ° C

(Polyamine resin (A-2)) Composition: dicarboxylic acid component unit (terephthalic acid: 62.5 mol%, adipic acid: 37.5 mol%), diamine component unit (1,6-hexanediamine: 100 mol%) Ultimate viscosity [η]: 1.0 dl/g Melting point: 320 ° C

(Polyamine resin (A-3)) Composition: dicarboxylic acid component unit (terephthalic acid: 55 mol%, adipic acid: 45 mol%), diamine component unit (1,6-hexanediamine: 100 mol%) Ultimate viscosity [η]: 0.8 dl/g Melting point: 310 ° C

(Polyamine resin (A-4)) Composition: dicarboxylic acid component unit (terephthalic acid: 55 mol%, adipic acid: 45 mol%), diamine component unit (1,6-hexanediamine: 100 mol%) Ultimate viscosity [η]: 1.0 dl/g Melting point: 310 ° C

[Flame retardant (B)] Manufactured by Clariant (Japan), EXOLIT OP1230 (phosphorus content: 23.8 wt%)

[Fatty acid metal salt (C)] Calcium montanate (trade name: Licomont CaV102, manufactured by Clariant (Japan)) Barium stearate (Ba-St), aluminum stearate (Al-St), calcium stearate (Ca-St), lithium pentadioate (Li-Beh), calcium behenate (Ca-Beh) ), lithium montanate (Li-Mon), zinc montanate (Zn-Mon): The above is manufactured by Nitto Chemical Industry Co., Ltd.

The following fatty acid ester compound and fatty acid guanamine compound were used for the comparison of the fatty acid metal salt compound.

Fatty acid ester of pentaerythritol: (Nissan Elector WEP-5, manufactured by Nippon Oil & Fats Co., Ltd.) Ethylene screw erucic acid AMAIDO: (Alflow AD-221P, manufactured by Nippon Oil & Fats Co., Ltd.)

[Reinforcing material (D)] Glass fiber (manufactured by CENTRAL GLASS, ECS03-615) Talc (made by Matsumura Industry Co., Ltd., trade name: Hifiller # 100 white clay 95)

The content of talc was 0.7 wt% with respect to the total of the polyamide resin (A), the flame retardant (B), the fatty acid metal salt (C), the reinforcing material (D), and talc.

[Examples 1 to 9] and [Comparative Examples 1 to 9] Each of the above components was mixed in an amount ratio shown in Tables 1 and 2, and placed in a biaxial extruder equipped with a vent hole set to a temperature of 320 ° C, and melt-kneaded to obtain a pelletized composition. Next, the respective characteristics of the obtained flame-retardant polyamine composition were evaluated. The results are shown in Tables 1 to 3.

Next, dry blending was carried out by adding 0.25 parts by weight of the fatty acid metal salt (C) shown in Table 4 to 99.75 parts by weight of the polyamine resin composition obtained in Example 2. The blended composition is injection molded. The flow length was measured in the same manner as above, and the amount of gas generated at the time of molding was visually evaluated. The case where no gas was generated was evaluated as ○, and the case where a plurality of gases were generated was evaluated as Δ, and the amount of gas generated was large, and the problem of use was evaluated as ×.

The resin composition having excellent thermal stability has a small gas generation amount and is difficult to cause contamination of the metal mold. Therefore, it is judged that the moldability is good. The results of each evaluation are shown in Table 4.

The carbon number of calcium stearate (Comparative Examples 10 and 11) was smaller than the carbon number of lithium dodecanoate or the carbon number of calcium montanate, and the melting point was also the lowest. Therefore, there is a phenomenon in which the amount of gas generated is increased.

The present invention claims priority based on the application number JP2007-90371 filed on March 30, 2007. The contents disclosed in the specification and drawings of the application are all cited in the specification of the present application.

[Industrial availability]

The flame-retardant polyamine composition of the present invention does not use a halogen-based flame retardant, has mechanical properties such as toughness, is excellent in heat resistance, flame retardancy, and fluidity in the reflow soldering step, and is thermally stable during molding. Good sex.

In particular, thin-walled molded articles such as fine-pitch connectors are well used for electrical assembly of parts by surface encapsulation using high-melting solder such as lead-free solder. Used in electronic applications or in the field of precision forming.

While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

Fig. 1 is a graph showing the relationship between temperature and time in a reflow step in a reflow heat resistance test carried out in Examples and Comparative Examples.

Claims (10)

A flame-retardant polyamine composition comprising: 20% by weight to 80% by weight of a polyamide resin (A), 10% by weight to 20% by weight of a halogen-free flame retardant (B), 0.1% by weight to 0.8% a wt% fatty acid metal salt (C), and 0 wt% to 50 wt% of a reinforcing material (D); the above flame retardant (B) is a phosphinic acid metal salt, and the above fatty acid metal salt (C) is selected from the group consisting of montanic acid One or a mixture of two or more of lithium, calcium, barium, zinc or aluminum salts of stearic acid or stearic acid other than calcium stearate and aluminum stearate. The flame-retardant polyamine composition according to claim 1, wherein the polyamide resin (A) comprises a polyfunctional carboxylic acid component unit (a-1) and a carbon number of 4 to 25 The polyfunctional amine component unit (a-2), wherein 60 mol% to 100 mol% of the polyfunctional carboxylic acid component unit (a-1) is a terephthalic acid component unit, and 0 mol% to 40 mol% is a terephthalic acid unit. The aromatic polyfunctional carboxylic acid component unit is 0 mol% to 40 mol% of an aliphatic polyfunctional carboxylic acid component having 4 to 20 carbon atoms. The flame-retardant polyamine composition according to claim 1, wherein the polyamide resin (A) has a melting point of 280 ° C to 340 ° C and an ultimate viscosity measured in concentrated sulfuric acid at 25 ° C. [η] is from 0.5 dl/g to 0.95 dl/g. The flame-retardant polyamine composition according to claim 1, wherein the flame retardant (B) is an aluminum salt of diethylphosphinic acid. The flame-retardant polyamine composition according to claim 1, wherein the fatty acid metal salt (C) is selected from the group consisting of calcium montanate and lignite. One or a mixture of two or more of the group consisting of zinc acid, barium stearate, calcium behenate and lithium behenate. The flame-retardant polyamine composition according to claim 5, wherein the fatty acid metal salt (C) is one or a group selected from the group consisting of calcium montanate and lithium hexate. the above. A molded body obtained by molding the flame-retardant polyamine composition as described in claim 1 of the patent application. An electronic component obtained by molding a flame-retardant polyamine composition as described in claim 1 of the patent application. A method for producing a flame-retardant polyamine composition according to the first aspect of the invention, comprising: mixing a metal phosphinate (B) and a fatty acid metal salt in a polymer of the polyamide resin (A) a step (C); and a step of extruding the mixture in a molten state. A method for producing a flame-retardant polyamine composition according to claim 1, comprising: preparing a polyamide resin (A) and a flame retardant (B), and optionally a reinforcing material (D) a resin composition; a step of adding a fatty acid metal salt (C) to the resin composition; and a step of injection molding the resin composition to which the fatty acid metal salt (C) is added.